CN112062231A - Electrode active material capable of selectively adsorbing copper ions, electrode plate and application - Google Patents

Electrode active material capable of selectively adsorbing copper ions, electrode plate and application Download PDF

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CN112062231A
CN112062231A CN202010896477.8A CN202010896477A CN112062231A CN 112062231 A CN112062231 A CN 112062231A CN 202010896477 A CN202010896477 A CN 202010896477A CN 112062231 A CN112062231 A CN 112062231A
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copper ions
active material
ions
electrode
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CN112062231B (en
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周宏建
高勇
张云霞
张海民
汪国忠
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Hefei Institutes of Physical Science of CAS
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4691—Capacitive deionisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

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  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
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  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
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  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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Abstract

The invention discloses an electrode active material for selectively adsorbing copper ions, which consists of nitrogen-sulfur-doped carbon and iron disulfide loaded by the nitrogen-sulfur-doped carbon; the invention also discloses an electrode slice, wherein the active material of the electrode slice is the electrode active material which selectively adsorbs copper ions; the invention also discloses a capacitive deionization module, which comprises the electrode plate; the invention also discloses application of the capacitive deionization module. The invention obtains the nitrogen-sulfur-doped carbon-loaded iron disulfide FeS by calcining and vulcanizing the MOF material with iron as a central atom2The material is taken as a capacitive deionization material, and the carbon-doped loaded iron disulfide material has good selective adsorption to copper ionsThe electrode active material in the module improves the adsorption selectivity of the capacitance deionization module to copper ions, and can be applied to removal of the copper ions in drinking water or industrial wastewater.

Description

Electrode active material capable of selectively adsorbing copper ions, electrode plate and application
Technical Field
The invention relates to the technical field of water treatment, in particular to an electrode active material for selectively adsorbing copper ions, an electrode plate and application.
Background
Heavy metals are metals with a specific gravity of more than 5, and about 45 kinds of heavy metals include mercury, cadmium, copper, lead and the like. At present, heavy metals are recognized as one of the most environmentally threatening pollutants due to their undegradability and enrichment. Most heavy metals in the environment can harm the ecological environment and human health when being excessively existed, and a great deal of toxicological and epidemiological researches prove that the biotoxicity of five of the heavy metals, namely lead, chromium, cadmium, mercury and arsenic is most obvious. In addition, copper, manganese, zinc, nickel and the like are trace elements necessary for human bodies, but the excessive intake of copper, manganese, zinc, nickel and the like can cause damage to the health of the human bodies.
The following methods for removing heavy metals from drinking water or industrial wastewater include chemical precipitation, membrane filtration, ion exchange, carbon material adsorption, and electrochemical processes. However, these methods have their own advantages and limitations. For example, high cost, complex operation, many side reactions, high energy consumption and the like. As a new technology for desalination and water purification, Capacitive Deionization (CDI) is an electro-adsorption process that uses a low electric field to adsorb charged ions onto the electric double layer of two porous electrodes, thereby achieving the removal of charged ions in an aqueous solution. Compared with the processes such as membrane filtration, chemical precipitation and the like, the capacitive deionization technology has the advantages of high energy efficiency, simplicity in operation, low cost and the like. Moreover, the electrode can regenerate the electrode material in situ by means of open circuit, short circuit or reverse voltage, thereby realizing heavy metal recovery and recycling of the electrode material, and simultaneously reducing the problems of dirt and scale formation to the minimum.
In CDI devices, the performance of CDI depends to a large extent on the properties of the electrode material selected, and therefore the development of suitable electrode active materials is a key factor in its development.
Disclosure of Invention
The invention provides a selective absorberAn electrode active material with copper ions is prepared by calcining and sulfurizing the MOF material with Fe as central atom to obtain the composite FeS material composed of N-S doped carbon and Fe disulfide2@ NSC, this iron disulfide material that mixes carbon load has fine selectivity adsorptivity to copper ion, regard this material as the electrode active material in the electric capacity deionization module, has improved the adsorption selectivity of electric capacity deionization module to copper ion, can be applied to getting rid of copper ion in drinking water or the industrial waste water.
The invention provides an electrode active material for selectively adsorbing copper ions, which consists of nitrogen-sulfur-doped carbon and iron disulfide loaded by the nitrogen-sulfur-doped carbon.
In the present invention, the electrode active material is FeS2@ NSC denotes, wherein "FeS2"denotes iron disulfide," @ "denotes a load, and" NSC "denotes nitrogen-sulfur-doped carbon.
Preferably, the electrode active material is obtained by calcining and vulcanizing an MOF material with iron as a central atom; wherein the calcined product consists of nitrogen-doped carbon and iron loaded on the nitrogen-doped carbon.
In the present invention, the calcined product is represented by Fe @ NC, "Fe" represents an iron simple substance, "@" represents a load, and "NC" represents nitrogen-doped carbon.
Preferably, the MOF material taking iron as a central atom is one or a mixture of more than two of MIL-88(Fe), MIL-100(Fe), MIL-101(Fe), MIL-127(Fe) and MIL-53 (Fe).
Preferably, the calcination temperature is 600 ℃ and the calcination time is 2 h.
Preferably, the temperature is raised to 600 ℃ at a rate of 5 ℃/min.
Preferably, the vulcanizing agent is sulfur powder.
Preferably, the vulcanization temperature is 500 ℃ and the vulcanization time is 2 h.
The MOF material is prepared by taking an iron source and an organic ligand as raw materials and adopting a hydrothermal method or an oil bath method.
The hydrothermal method comprises the following specific preparation processes:
respectively dissolving an iron source and an organic ligand in a dimethylformamide solution, respectively carrying out ultrasonic treatment, transferring the solution to a reaction kettle, putting the reaction kettle into the reaction kettle, heating the reaction kettle to 130 ℃, reacting for 12-24h, naturally cooling, centrifuging, washing with deionized water and the dimethylformamide solution for several times, and drying at 70-80 ℃ to obtain the MOF material.
The organic ligand in the hydrothermal method can be one of terephthalic acid, diamino terephthalic acid and fumaric acid.
The oil bath method comprises the following specific preparation processes:
mixing an iron source and an organic ligand, reacting for 12-24h under an oil bath at 80 ℃, centrifugally washing precipitates by using deionized water and ethanol, and drying at 70-80 ℃ to obtain the MOF material.
The organic ligand in the oil bath method can be selected from fumaric acid, diamino terephthalic acid, terephthalic acid or fumaric acid.
The iron source in the hydrothermal method and the oil bath method is ferric chloride, copper sulfate or ferric nitrate.
The invention also provides an electrode slice, and the active material of the electrode slice is the electrode active material for selectively adsorbing copper ions.
Preferably, the conductive agent in the electrode plate is acetylene black, carbon black or ketjen black; the adhesive is polyvinylidene fluoride, polytetrafluoroethylene or naphthol; the current collector is carbon paper, carbon felt or titanium sheet.
The preparation method of the electrode slice comprises the following steps: FeS is prepared2The @ NSC material, the conductive agent and the adhesive are mixed according to the mass ratio of 80-95: 10: 10, adding the mixture into a solvent, and stirring to obtain electrode slurry; then the electrode slurry is evenly coated on a current collector (the effective area is 4 multiplied by 4 cm)2) And finally drying at 70 ℃ to obtain the required electrode slice.
The invention also provides a capacitive deionization module, which comprises the electrode plate; the electrode plate is connected with a negative electrode at the capacitance deionization module.
Preferably, the electrode plate also comprises an active carbon as an active material; the electrode plate is connected with the anode at the capacitance deionization module.
The electrode sheet of the present invention using activated carbon as an active material can be manufactured by the same method as described above, except that the active material is replaced with activated carbon.
The invention also provides application of the capacitive deionization module, which is used for selectively adsorbing or removing copper ions in the solution.
Preferably, the concentration of copper ions in the solution is 10-400 mg/L.
Preferably, the solution further comprises one or a mixture of two or more of sodium ions, lead ions, zinc ions, manganese ions, cobalt ions and cadmium ions in addition to the copper ions.
Preferably, the working voltage of the capacitive deionization module is 0.8-1.4V.
The specific adsorption process of the capacitance deionization module on copper ions is as follows: and (3) conveying the solution containing copper ions to the capacitance deionization module through a peristaltic pump, wherein the flow rate of the peristaltic pump is controlled to be 20 mL/min.
The electrode plate is used in a capacitive deionization module, has excellent adsorption selectivity on copper ions, particularly has high selectivity on copper ions in a sodium ion-containing mixed solution or a lead ion-containing mixed solution, zinc ions, cadmium ions, manganese ions and cobalt ions, has excellent copper ion removal performance, still maintains good adsorption capacity and copper ion adsorption selectivity after being recycled for multiple times, and has good application prospect in the field of water treatment.
Drawings
FIG. 1 shows the calcined product Fe @ NC and the vulcanized product FeS obtained in example 12The XRD pattern of @ NSC.
FIG. 2 is an SEM image of the Fe @ NC material obtained in example 1.
FIG. 3 shows FeS obtained in example 12SEM image of @ NSC material.
FIG. 4 shows FeS obtained in example 12High resolution XPS plots of @ NSC material; (a) fe 2p, (b) S2 p, (C) C1S and (d) N1S.
FIG. 5 is an XRD pattern of MIL-88(Fe) from example 1 and MIL-101(Fe) from example 2.
Figure 6 is an XRD pattern of the cured product of example 1, example 3 and example 4.
FIG. 7(a) shows FeS obtained in example 12The removal amount of copper ions in a solution with the copper ion concentration of 10ppm by adopting the @ NSC material under different voltages; (b) the FeS obtained in example 1 was adjusted to 1V2The @ NSC material removes copper ions from copper ion solutions of different concentrations.
FIG. 8 is an XPS plot of copper on the electrode sheet obtained in example 8 after 100ppm of copper ion solution was electro-adsorbed at 1V, wherein (a) is Cu 2p3/2(ii) a (b) Is Cu LMM.
FIG. 9 shows FeS obtained in example 12XPS plot of Fe 2p after electroadsorption for @ NSC material.
FIG. 10 shows commercial Activated Carbon (AC), calcined product (Fe @ NC) obtained in example 1, and vulcanized product (FeS) obtained in example 12@ NSC) effect on removal of copper ions from a solution having a copper ion concentration of 100 ppm.
FIG. 11(a) shows FeS obtained in example 12The XRD pattern after cycling for the @ NSC material; (b) FeS for example 12@ NSC material removes copper ions during ten cycles in a solution having a copper ion concentration of 10 ppm.
FIG. 12 shows FeS obtained in example 12The removal amount of copper ions in the mixed ion solution of copper ions and sodium ions with different molar ratios is @ NSC material.
FIG. 13 shows FeS obtained in example 12The removal effect of @ NSC material on copper ions in a mixed ion solution containing copper ions, lead ions, zinc ions, manganese ions, cobalt ions and cadmium ions, wherein (a) is the removal efficiency over time; (b) is the amount removed.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of a nitrogen-sulfur-doped carbon-loaded iron disulfide material comprises the following steps:
respectively dissolving 0.66mol of ferric nitrate nonahydrate and 0.66mol of diaminoterephthalic acid in 30mL of dimethylformamide solution, respectively carrying out ultrasonic treatment, then transferring to a reaction kettle, heating the reaction kettle to 130 ℃, keeping the temperature for 24h, naturally cooling, centrifuging, washing with deionized water and the dimethylformamide solution for several times, and drying at 70 ℃ to obtain reddish brown MIL-88(Fe) powder;
heating the reddish brown MIL-88 powder to 600 ℃ at the speed of 5 ℃/min, and calcining for 2h to obtain Fe @ NC;
mixing Fe @ NC with sulfur powder, wherein the mass ratio of Fe @ NC to sulfur powder is 1: 5, introducing nitrogen, heating to 500 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 2 hours to finally obtain the composite material FeS consisting of the nitrogen-sulfur doped carbon and the loaded iron disulfide2@NSC。
Calcined product Fe @ NC and sulfurized product FeS obtained in example 12The XRD pattern of the @ NSC material is shown in FIG. 1; the SEM image of the Fe @ NC material is shown in FIG. 2; FeS2The SEM image of the @ NSC material is shown in FIG. 2.
From fig. 2 it can be seen that the Fe @ NC material has a doped carbon (leaf-shaped structure in the figure) and its supported elemental iron (fine-grained structure in the figure).
From FIG. 3, it can be seen that FeS2The @ NSC consists of doped carbon (diamond structure in the figure) and its supported iron disulfide (particle structure in the figure).
FeS from example 12The high resolution XPS plot of the @ NSC material is shown in FIG. 4, where (a) Fe 2p, (b) S2 p, (C) C1S and (d) N1S; from FIG. 4, the FeS can be derived2@ FeS in NSC material2Composition and N, S co-doping with the presence of carbon structures.
Example 2
A preparation method of a nitrogen-sulfur-doped carbon-loaded iron disulfide material comprises the following steps:
10mmo1 of FeC13·6H2Mixing O and 10mmo1 fumaric acid uniformly, reacting for 12h under 80 ℃ oil bath, centrifugally washing precipitate with deionized water and ethanol until washing liquid is transparent, and drying at 70 ℃ to obtain MIL-101 (Fe);
heating MIL-101 to 600 ℃ at the speed of 5 ℃/min, and calcining for 2h to obtain Fe @ NC;
mixing Fe @ NC with sulfur powder, wherein the mass ratio of Fe @ NC to sulfur powder is 1: 5, introducing nitrogen gas toRaising the temperature to 500 ℃ at the temperature raising rate of 5 ℃/min, and keeping the temperature for 2 hours to finally obtain the FeS composite material consisting of the nitrogen-sulfur doped carbon and the iron disulfide loaded by the carbon2@NSC。
The XRD patterns of MIL-88(Fe) obtained in example 1 and MIL-101(Fe) obtained in example 2 are shown in FIG. 5.
Example 3
Same as example 1 except that the vulcanization temperature was 550 ℃.
Example 4
The same as in example 1, except that the vulcanization temperature was 600 ℃.
The XRD patterns of the sulphidic products obtained in examples 1, 3 and 4 are shown in FIG. 6, from which it can be seen that iron is present in the sulphidic product in the form of Fe at a sulphidation temperature of 600 ℃7S8When the sulfidation temperature is 550 ℃, the iron in the sulfidation product is present in the form of Fe7S8And FeS2Only when the vulcanization temperature is 500 ℃ to form FeS2。
Example 5
Same as example 1 except that ferric nitrate nonahydrate was changed to ferric chloride tetrahydrate.
Example 6
Same as example 1 except that diaminoterephthalic acid was changed to terephthalic acid.
Example 7
Same as example 1 except that diaminoterephthalic acid was changed to fumaric acid.
Example 8
The preparation process of the electrode plate comprises the following steps:
adding the nitrogen-sulfur-doped carbon-loaded iron disulfide material prepared in example 1, polyvinylidene fluoride and ketjen black into a dimethylformamide solution according to the mass ratio of 8:1:1, mixing, stirring to obtain electrode slurry, and uniformly coating the electrode slurry on a titanium electrode sheet (the effective area is 4 multiplied by 4 cm)2) Finally, the obtained product is put into a 70 ℃ oven to be dried overnight to obtain the required electrode slice.
Example 9
Same as example 8 except that polyvinylidene fluoride was changed to polytetrafluoroethylene.
Example 10
Same as example 8 except that polyvinylidene fluoride was changed to naphthol.
Example 11
A method for selectively adsorbing copper ions in a solution, comprising the steps of:
the positive plate obtained by using the activated carbon as the positive active material and by the same method as in example 8 and the negative plate obtained in example 8 were assembled into a capacitive deionization module, and then the solution containing copper ions was transferred to the capacitive deionization module by a peristaltic pump to adsorb the copper ions.
To verify the FeS obtained by the present invention2The adsorption performance of the @ NSC material on copper ions is tested, and the FeS obtained in example 1 is tested under different voltage conditions2The effect of the @ NSC material on the removal of copper ions from a solution having a copper ion concentration of 10ppm, and FeS at a voltage of 1V2The removal effect of the @ NSC material on copper ions in copper ion solutions with different concentrations is shown in FIG. 7. It can be seen from FIG. 7(a) that in the solution having a copper ion concentration of 10ppm, the amount of copper ion removed increases with increasing voltage (0.8-1.4V); as is clear from FIG. 7(b), the amount of copper ions removed is the greatest when the concentration of copper ions is 300ppm at a voltage of 1V.
The XPS spectra of copper and iron before and after adsorption of the negative electrode sheet obtained in example 8 were analyzed for Cu 2p (a) in FIG. 8 as shown in FIGS. 8 and 9, respectively, by selecting a solution having a copper ion concentration of 100ppm as the test solution3/2(ii) a (b) The XPS spectrum of the Cu LMM shows that copper deposition cannot occur under the voltage of 1V; further, FeS before adsorption in FIGS. 9 and 4(a)2Comparison of XPS plots of Fe 2p in @ NSC revealed that the trivalent iron content increased after adsorption, and from FIG. 8, it was found that the higher trivalent iron content was attributed to FeS during adsorption2The ferrous iron in the @ NSC material reduces the divalent copper, thereby illustrating that there is a redox reaction in the electro-adsorption, and part of the divalent copper in fig. 8 is adsorbed by the electric double layer.
Comparative example 1
A method for selectively adsorbing copper ions in a solution, comprising the steps of:
the negative electrode sheet obtained by using the vulcanization product Fe @ NC obtained in example 1 as a negative electrode active material and the same method as in example 8, and the positive electrode sheet obtained by using commercial Activated Carbon (AC) as a positive electrode active material and the same method as in example 8 were assembled to form a capacitive deionization module, and then a solution containing copper ions was transferred to the capacitive deionization module by a peristaltic pump to adsorb the copper ions.
Comparative example 2
A method for selectively adsorbing copper ions in a solution, comprising the steps of:
the electrode sheets obtained by using commercial Activated Carbon (AC) as a positive electrode active material and using the same method as in example 8 were used as a positive electrode sheet and a negative electrode sheet to prepare a capacitive deionization module, and then the copper ion-containing solution was transferred to the capacitive deionization module by a peristaltic pump to adsorb copper ions.
The effect of example 8 and control 1-2 on copper ion removal is shown in FIG. 10, from which FIG. 10 it can be seen that FeS is comparable to commercial Activated Carbon (AC) and sulfidation product (Fe @ NC)2The @ NSC material has better effect of removing copper ions, and the removal amount is obviously improved.
In order to test the FeS obtained in the present application2@ NSC Material for Cyclic stability against copper ion adsorption FeS obtained in example 12The results of the @ NSC material cyclically adsorbing copper ions are shown in FIG. 11. FIG. 11(a) shows FeS2The XRD pattern after cycling for the @ NSC material; (b) is FeS2The effect of the @ NSC material on removal of copper ions was achieved by circulating the material ten times in a solution containing 10ppm of copper ions, and as is clear from FIG. 12, the FeS obtained in example 1 was analyzed2The @ NSC material has the advantages that XRD (X-ray diffraction) is not obviously changed after being recycled for many times, the stability of the material is good, the good adsorption quantity of copper ions is still kept, and the good cyclic adsorption stability is realized.
Further, to test the FeS obtained according to the invention2Selectivity of @ NSC material for copper ion adsorption FeS obtained in example 12@ NSC material for copper ion and sodium ion mixed ion solution with different proportions and copper ion, lead ion and zinc ion containing solutionThe adsorption test was performed in the mixed ion solution of the manganese ion, the cobalt ion and the cadmium ion, and the test results are shown in fig. 12 and 13.
As can be seen from the analysis of FIG. 12, FeS was contained in a mixed ion solution containing copper ions and sodium ions at different molar ratios2The @ NSC material always keeps good adsorption capacity to copper ions, and has high selectivity to copper ions compared with sodium ions.
From the analysis of FIG. 13, it is found that Cu2+、Pb2+、Cd2+、Zn2+、Mn2+、Co2+In mixed ion solution of (2), FeS2The @ NSC material appears to be Cu2+The high selectivity of (a) is much greater for the adsorption of copper ions than for other ions, and the selective adsorption of copper ions is maintained over adsorption time.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (10)

1. An electrode active material for selectively adsorbing copper ions is characterized by consisting of nitrogen-sulfur doped carbon and iron disulfide loaded by the nitrogen-sulfur doped carbon.
2. The electrode active material for selectively adsorbing copper ions according to claim 1, wherein the electrode active material is obtained by calcining and vulcanizing an MOF material having iron as a central atom; wherein the calcined product consists of nitrogen-doped carbon and iron loaded on the nitrogen-doped carbon.
3. The electrode active material for selective adsorption of copper ions according to claim 1 or 2, wherein the MOF material having iron as a central atom is one or a mixture of two or more of MIL-88(Fe), MIL-100(Fe), MIL-101(Fe), MIL-127(Fe), MIL-53 (Fe);
preferably, the calcining temperature is 600 ℃, and the calcining time is 2 h;
preferably, the temperature is raised to 600 ℃ at the speed of 5 ℃/min;
preferably, the vulcanizing agent is sulfur powder;
preferably, the vulcanization temperature is 500 ℃ and the vulcanization time is 2 h.
4. An electrode sheet characterized in that the active material thereof is the electrode active material for selectively adsorbing copper ions according to any one of claims 1 to 3.
5. The electrode sheet according to claim 4, wherein the conductive agent in the electrode sheet is acetylene black, carbon black or ketjen black; the adhesive is polyvinylidene fluoride, polytetrafluoroethylene or naphthol; the current collector is carbon paper, carbon felt or titanium sheet.
6. A capacitive deionization module comprising the electrode sheet according to claim 4 or 5.
7. The capacitive deionization module of claim 6, further comprising an electrode sheet using activated carbon as an active material.
8. Use of a capacitive deionization module as claimed in claim 6 or 7 for the selective adsorption or removal of copper ions from a solution.
9. Use of a capacitive deionization module according to claim 8, wherein the concentration of copper ions in the solution is 10-400 mg/L.
10. Use of a capacitive deionization module according to claim 8 or 9, wherein the solution comprises, in addition to copper ions, one or a mixture of two or more of sodium ions, lead ions, zinc ions, manganese ions, cobalt ions and cadmium ions.
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CN113511710A (en) * 2021-05-27 2021-10-19 安徽中科索纳新材料科技有限公司 Electrode active material for capacitance adsorption of lead ions and preparation method and application thereof
CN113511635A (en) * 2021-03-17 2021-10-19 合肥学院 Porous iron selenide carbon-coated composite material and application thereof in potassium ion battery
CN114349133A (en) * 2022-01-13 2022-04-15 东莞理工学院 Preparation method of copper sulfide electrode material and application of copper sulfide electrode material in sewage copper extraction
CN115231763A (en) * 2022-07-21 2022-10-25 湖南金龙新材料有限公司 Treatment method of copper-containing circulating cooling water

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